[go: up one dir, main page]

WO2005016987A1 - Compositions reticulables a enthalpie reduite - Google Patents

Compositions reticulables a enthalpie reduite Download PDF

Info

Publication number
WO2005016987A1
WO2005016987A1 PCT/IE2004/000099 IE2004000099W WO2005016987A1 WO 2005016987 A1 WO2005016987 A1 WO 2005016987A1 IE 2004000099 W IE2004000099 W IE 2004000099W WO 2005016987 A1 WO2005016987 A1 WO 2005016987A1
Authority
WO
WIPO (PCT)
Prior art keywords
heat absorbing
absorbing component
reaction
component
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IE2004/000099
Other languages
English (en)
Inventor
Barry Burns
Jonathan Wigham
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Loctite Ireland Ltd
Original Assignee
Henkel Loctite Ireland Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Loctite Ireland Ltd filed Critical Henkel Loctite Ireland Ltd
Publication of WO2005016987A1 publication Critical patent/WO2005016987A1/fr
Anticipated expiration legal-status Critical
Priority to US12/026,221 priority Critical patent/US20080177023A1/en
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates generally to curable compositions and in particular to the field of adhesives.
  • curable compositions which, during cure, undergo exothermic reaction, such as epoxy compositions, in particular one-part epoxy compositions.
  • thermodynamics of many curable adhesive systems are such that the enthalpy change can be quite large.
  • the exotherm is not of concern as cure occurs under suitable conditions for the end use application of the curable adhesive system.
  • the cure exotherm may be of concern where cure may occur under conditions which are not controlled, such as during transportation or storage.
  • the storage system comprises a container vessel, a removable heat sink material adapted to hold, and be in intimate contact with, one or more packages of exothermic material.
  • the heat sink material has an effective heat capacity and latent heat of melting and/or vaporization such that it absorbs all of the energy produced by the exothermic material if it reacts by reaching its reaction initiation temperature.
  • Cooling means can also be provided in the vessel and surrounding the heat sink material and packaged exothermic material. It is to be noted that the package is designed to absorb the heat given out by the reaction rather than to reduce the overall amount of heat evolved during chemical reaction of the composition.
  • compositions An alternative method of reducing the risks posed by such compositions has been to include in the compositions one or more components, which might reduce the exothermic effect.
  • a first method involves the addition of a reactive component in the composition, to take part in the curing reaction so as to form part of the chemical structure of the cured product.
  • the reactive component is selected to alter the thermodynamics of the cure process so that a modified exothermic reaction occurs which will liberate less heat.
  • the second main method involves the inclusion in the composition of an inert filler component such as talc, calcium carbonate, alumina or silica as a filler material.
  • an inert filler component such as talc, calcium carbonate, alumina or silica.
  • the inert filler materials do not take part in the cure reaction, acting only to "bulk out” the composition so that there is less curable material and curing agent therefor per unit area, the fillers act to "dilute” the curable composition, thus reducing the amount of heat given out per unit volume of composition.
  • These compounds reduce the ⁇ H (exotherm) value purely in terms of replacing a mass of reactive (epoxy) groups with a non-reactive inert material.
  • such fillers are included in amounts up to 70 parts by weight of the composition before they will reduce the exotherm heat sufficiently. In such amounts they may deleteriously affect the properties of the cured material. For that reason and others it is desirable not to include large amounts of these materials in the composition.
  • U.S. Patent No. 6,270,836 describes gel-coated microcapsules which have improved mechanical stress- and flame-resistance.
  • the document refers to the inclusion of phase change materials in the microcapsules to provide thermal control in a wide variety of environments such as in protective clothing. In all respects the '836 patent is concerned with the protection of manufactured articles from subsequent exposure to heat.
  • the document also describes the incorporation of microcapsules within a base material such as epoxy.
  • Phase change materials referred to in the patent are parrafinic hydrocarbons of formula C n H n+2 where n is 20 to 30.
  • Other phase change materials referred to are 2,2- dimethyl-l,3-propanediol (DMP), and 2-hydroxymethyl-2-methyl-l,3-propanediol
  • microcapsules are said to be useful to incorporate in many compositions including potting compositions and epoxy materials but the main teaching of the document is to providing a foamed organic material that can be inco ⁇ orated into an article of clothing or footwear.
  • the adhesive composition comprises ethylene vinyl acetate copolymer, modified petroleum resin which has some epoxylated double bonds, naphthenic oil, tackifier, crystal phase wax, and antioxidants.
  • U.S. Patent No. 6,121,348 (White) relates to a heat curable, solid epoxy resin for use in powder form.
  • This patent is concerned with the properties of the powder form of the epoxy resin in particular in providing compositions with a melting point of at least 55 C.
  • the composition includes epoxy resin or epoxy containing material; a solidifying amine system for the epoxy material; a hardener for the epoxy material; an expanding agent and other optional additives.
  • Expanding agents disclosed are azodicarbonamide, azodiisobutyronitrile, benzene sulphonhydrazide, dinitroso pentamethylene tetramine, oxybis benzene sulphonhydrazide, p toluene sulphonyl hydrazide and expandable plastic such as those sold under the trade name EXPANCEL.
  • EXPANCEL is a registered trade mark for microspheres which are small spherical plastic particles. The microspheres consist of a polymer shell encapsulating a gas. When the gas inside the shell is heated, it increases its pressure and the thermoplastic shell softens, resulting in a dramatic increase in the volume of the microspheres (by a factor of 40).
  • formulations having a high exotherm are undesirable.
  • epoxy adhesive compositions are known to be highly exothermic.
  • Such formulations having a high exotherm are undesirable for practical reasons, including difficulties with storage and transport, for example, as discussed above.
  • curable compositions having a reduced exotherm.
  • a heat absorbing component which can be incorporated into curable compositions in order to effectively reduce the exotherm without interfering with the cure mechanism and/or without affecting the cured adhesive properties.
  • the invention provides a curable composition useful for instance as adhesives, sealants and coatings.
  • Commercial applications of the inventive compositions include use as underfills; chip bonders; glob tops; encapsulants; potting materials; die attach materials and the like.
  • compositions comprise: (i) a curable component
  • a curing agent component for curing the curable component, the cure reaction being exothermic (ii) a curing agent component for curing the curable component, the cure reaction being exothermic; and (iii) an inert heat absorbing component dispersed throughout the composition for absorbing heat generated by the exothermic reaction in an amount sufficient to achieve at least one of the conditions selected from the group of conditions consisting of : (a) decrease the heat given out by the reaction by at least 10%, the amount of heat absorbing component being less than 20% by weight of the total composition; (b) the heat absorbing component having a melting point in the range of temperatures from the cure onset temperature to the end temperature of reaction; and 7 (ii) a curing agent component for curing the curable component, the cure reaction being exothermic; and
  • an inert heat absorbing component dispersed within the composition for absorbing heat generated by the exothermic reaction, the heat absorbing component having a latent heat of fusion of greater than or equal to 20J/g.
  • the invention also provides a method for selecting a heat absorbing component for addition to a curable composition which cures with an exotherm.
  • the method comprises the steps of - (i) providing a curable component; and (ii) comparing the temperature range of the cure exotherm of the curable component to the melting point or melting range of a heat absorbing component and determining if the melting point or melting range of the heat absorbing component falls within the temperature range of the cure exotherm, and (iii) selecting the heat absorbing component if it has a melting point or melting range that falls within the temperature range of the cure exotherm of the curable component.
  • a curative for the cure component is present also.
  • a method of compensating for the heat given out on cure of an exothermically curable composition comprising the steps of (i) providing an exothermically curable composition;
  • the exothermically curable composition has an exotherm value of greater than 300 J/g and a sufficient amount of the heat absorbing component is added to reduce the exotherm value to less than 300 J/g.
  • the invention provides for the use of a heat absorbing component in the manufacture of a reactive curable composition having an exotherm value of greater than 300J/g before inclusion of the heat absorbing component, whereby the heat absorbing component is selected such that it has a melting point range in the temperature range from the cure onset temperature to the end temperature of reaction of the curable composition.
  • the heat absorbing component is present in an amount of 0.001-100 parts, preferably 0.1 - 40 parts by weight, more preferably in an amount of 1 -30 parts by weight.
  • the invention provides a heat cure epoxy formulation having an exotherm below 300 J/g.
  • the epoxy formulation according to the invention is therefore not classified as a self-reactive substance.
  • the present invention relates to reaction products of the curable composition of the present invention.
  • the cured product of the composition of the invention suitably comprises unreacted heat absorbing component trapped in the cured composition.
  • the cured products of the composition of the invention may be used as a chip bonders, underfills, encapsulants and the like.
  • An electronic component encapsulated with the cured product of the curable composition of the invention is also provided.
  • the invention further relates to a method of bonding two substrates comprising selecting two substrates, applying the curable composition of the invention to one of the substrates, wherein one substrate is an electronic circuit board and the other substrate is an electronic component, and bringing the two substrates together.
  • the invention further provides an underfilled product comprising an electronic component on a circuit board underfilled with the cured product of the curable composition of the invention.
  • Figure 1 shows a dynamic Differential Scanning Calorimetry (DSC) curve for the epoxy adhesive composition of Example 1 which does not contain a heat absorbing component;
  • Figure 2 shows a dynamic DSC curve for the epoxy adhesive composition of Example 2 which contains 10 parts by weight of talc;
  • Figure 3 shows a dynamic DSC curve for the epoxy adhesive composition of Example 3 which contains 10 parts by weight of polythene
  • Figure 4 shows a dynamic DSC curve for the epoxy adhesive composition of Example 4 which contains 20 parts by weight of polythene
  • Figure 5 shows a dynamic DSC curve for a re -scanned sample of the cured composition which produced the DSC shown in Figure 3 showing a melting endotherm corresponding to the melting point of polythene;
  • Figure 6 shows a dynamic DSC curve for a re-scanned sample of the cured epoxy adhesive composition which produced the DSC as shown in Figure 4 showing an endotherm corresponding to the melting point of polythene; 10
  • Figure 7 shows a dynamic DSC curve for the curable composition of Example 5 which does not contain a heat absorbing component
  • Figure 8 shows a dynamic DSC curve for the curable composition of Example 6 which contains 10 parts by weight of Thixcin R;
  • Figure 9 shows a dynamic DSC curve for the curable composition of Example 7 which contains 20 parts by weight of Thixcin R;
  • Figure 10 shows a dynamic DSC curve for the curable composition of Example 8 which does not contain a heat absorbing component
  • Figure 11 shows a dynamic DSC curve for the curable composition of Example 9 which contains 5 parts by weight of R 2526;
  • Figure 12 shows a dynamic DSC curve for the curable composition of Example 10 which contains 10 parts by weight of R 2526;
  • Figure 13 shows a dynamic DSC curve for the curable composition of Example 11 which does not contain a heat absorbing component
  • Figure 14 shows a dynamic DSC curve for the curable composition of Example 12 which contains 10 parts by weight of Paraflint C 80;
  • Figure 15 shows a dynamic DSC curve for the curable composition of Example 13 which contains 20 parts by weight of Paraflint SP 30 F;
  • Figure 16 shows a dynamic DSC curve for the curable composition of Example 14 which contains 10 parts by weight of R 2542; 11
  • Figure 17 shows a dynamic DSC curve for the curable composition of Example 15 which does not contain a heat absorbing component
  • Figure 18 shows a dynamic DSC curve for the curable composition of Example 16 which contains 20 parts by weight of talc;
  • Figure 19 shows a dynamic DSC curve for the curable composition of Example 17 which contains 10 parts by weight of polyethylene
  • Figure 20 shows a dynamic DSC curve for the curable composition of Example 18 which does not contain sulphur powder
  • Figure 21 shows a dynamic DSC curve for the curable composition of Example 19 which contains 10 parts by weight of sulphur powder.
  • the curable compositions according to the invention may comprise an inert heat absorbing component.
  • inert means that the heat absorbing component does not take part chemically in the cure reaction. The heat absorbing component remains unreacted following cure of the curable composition.
  • the curable composition cures by exothermic reaction with a cure exotherm profile from an onset temperature of reaction to a maximum temperature of reaction and with an end temperature of reaction.
  • the curable component is an epoxy component.
  • the epoxy compound for the epoxy resin compositions of the present invention may be selected from any polymeric epoxide which has an average of two or more epoxide 12 groups per molecule, including polyglycidyl ethers of polyhydric phenols, for example, polyglycidyl ethers of bisphenol A, bisphenol F, bisphenol AD, catechol, resorcinol.
  • polyglycidyl ethers of polyhydric phenols for example, polyglycidyl ethers of bisphenol A, bisphenol F, bisphenol AD, catechol, resorcinol.
  • Epoxy compounds obtained by reacting polyhydric alcohols such as butanediol or polyethylene glycol or glycerin with epichlorohydrin, are also suitable.
  • Epoxidised (poly) olefinic resins may also be used.
  • epoxidised phenolic novolac resins may also be used.
  • glycidyl ether esters such as those obtained by reacting hydroxycarboxylic acid with epichlorohydrin
  • polyglycidyl esters such as those obtained by reacting a polycarboxylic acid with epichlorohydrin.
  • Urethane modified epoxy resins are also suitable.
  • epoxy compounds include polyepoxy compounds based on aromatic amines and epichlorohydrin, such as N,N-diglycidyl-aniline; N, N -dimethyl-N, N'-diglycidyl- 4,4'diaminodiphenyl methane; N, N, N', N'-tetraglycidyl-4,4'diaminodiphenyl methane; N-diglycidyl-4-aminophenyl glycidyl ether; and N, N, N', N'-tetraglycidyl- 1,3 -propylene bis-4-aminobenzoate .
  • polyepoxy compounds based on aromatic amines and epichlorohydrin such as N,N-diglycidyl-aniline; N, N -dimethyl-N, N'-diglycidyl- 4,4'diaminodiphenyl methane; N, N, N', N'-tetrag
  • epoxy resins suitable for use herein are polyglycidyl derivatives of phenolic compounds, such as those available commercially under the trade names EPON 828, EPON 1001, EPON 1009, and EPON 1031, from Resolution Performance; DER 331, DER 332, DER 334, and DER 542 from Dow Chemical Co.; and BREN-S from Nippon Kayaku, Japan.
  • Other suitable epoxy resins include polyepoxides prepared from polyols and the like and polyglycidyl derivatives of phenol-formaldehyde novolacs, the latter of which are available commercially under the trade names DEN 431, DEN 438, and DEN 439 from Dow Chemical Company.
  • Cresol analogs are also available commercially ECN 1235, ECH 1273, and ECN 1299 from Vantico Inc.
  • SU-8 is a bisphenol A-type epoxy novolac available from Resolution Performance.
  • Polyglycidyl adducts of amines, aminoalcohols and polycarboxylic acids are also useful in this invention, commercially available resins of which include GLYAMINE 135, GLYAMINE 125, and GLYAMINE 115 from F. I. C. Corporation; ARALDITE MY-720, ARALDITE 0500, and ARALDITE 0510 from Vantico Inc. and PGA-X and PGA-C from the Sherwin-Williams Co.
  • Epoxy resins are discussed in U.S. Patent No.5,430,112 the entire contents of which are hereby incorporated herein. 13
  • Cyanate esters may also be used in the inventive compositions as the curable component, individually or in combination with another material.
  • the cyanate esters useful as a component in the inventive compositions may be chosen from dicyanatobenzenes, tricyanatobenzenes, dicyanatonaphthalenes, tricyanatonaphthalenes, dicyanato-biphenyl, bis(cyanatophenyl)methanes and alkyl derivatives thereof, bis(dihalocyanatophenyl)propanes, bis(cyanatophenyl)ethers, bis(cyanatophenyl)sulfides, bis(cyanatophenyl)propanes, tris(cyanatophenyl)phosphites, tris(cyanatophenyl)phosphates, bis(halocyanatophenyl)methanes, cyanated novolac, bis[cyanatophenyl(methylethylidene)]benzene, cyanated bisphenol
  • aryl compounds having at least one cyanate ester group on each molecule may be generally represented by the formula Ar(OCN) m , where Ar is an aromatic radical and m is an integer from 2 to 5.
  • the aromatic radical Ar should contain at least 6 carbon atoms, and may be derived, for example, from aromatic hydrocarbons, such as benzene, biphenyl, naphthalene, anthracene, pyrene or the like.
  • the aromatic radical Ar may also be derived from a polynuclear aromatic hydrocarbon in which at least two aromatic rings are attached to each other through a bridging group. Also included are aromatic radicals derived from novolac-type phenolic resins ⁇ z., cyanate esters of these phenolic resins.
  • Ar may also contain further ring-attached, non-reactive substituents.
  • cyanate esters include, for instance, 1,3-dicyanatobenzene; 1,4- dicyanatobenzene; 1,3-5-tricyanatobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7- dicyanatonaphthalene; 1,3,6-tricyanatonaphthalene; 4,4 -dicyanato-biphenyl; bis(4- cyanatophenyl)methane and 3 ',5-5 -tetramethyl bis(4-cyanatophenyl)methane; 2,2- bis(3,5-dichloro-4-cyanatophenyl) ⁇ ropane; 2,2-bis(3,5-dibromo-4- dicyanatophenyl)propane; bis(4-cyanatophenyl)ether; bis(4-cyanatophenyl)sulfide; 2,2- bis(4-cyanatophenyl)propane; tris(4-cyanatophenyl)
  • cyanate esters include cyanates disclosed in U.S. Patent Nos. 4,477,629 and 4,528,366, the disclosure of each of which is hereby expressly inco ⁇ orated herein by reference; the cyanate esters disclosed in U.K. Pat. No. 1,305,702, and the cyanate esters disclosed in International Patent Publication WO 85/02184, the disclosure of each of which is hereby expressly inco ⁇ orated herein by reference.
  • combinations of these cyanate esters within the imidazole component of the compositions of the present invention are also desirably employed herein.
  • the cyanate esters When used, the cyanate esters may be used in an amount of about 1 to about 20 weight percent. 15 Maleimides, nadimides, and itaconimides may be used as the curable component, either by themselves or in combination with another material (typically they are blended with an epoxy or cyanate ester), and include those compounds having the following structures I, II and III, respectively
  • R is independently selected from hydrogen or lower alkyl (C1-C5), and X is a monovalent moiety or a multivalent linking moiety comprising organic or organosiloxane radicals, and combinations thereof, such as siloxane/urethane block copolymers.
  • each R is independently as defined above, t falls in the range of 2 up to 10, u is 1, 2 or 3, and Ar is as defined above, or O il — Ar— Z— C — R or O
  • each Ar is a monosubstituted, disubstituted or trisubstituted aromatic or heteroaromatic ring having in the range of 3 up to about 10 carbon atoms; n is 1 up to about 50, and Z is selected from straight or branched chain alkyl, alkylene, oxyalkylene, alkenyl, alkenylene, oxyalkenylene, ester, or polyester, optionally containing substituents selected from hydroxy, alkoxy, carboxy, nitrile, cycloalkyl or cycloalkenyl; as well as combinations thereof.
  • the curing agent component is any suitable curing agent for the curable component.
  • the skilled person will therefore know which curing agent component to select with which curable component.
  • the curing agent is a latent one being activatable at a later time.
  • the latent curing agent is as described in U.S. Patent No. 5,430,112, assigned to Ajinomoto ("the '112 patent") and International Patent
  • the latent curing agent has a melting point in the range 80°C - 220°C, preferably 80°C-150°C and more preferably in the range 80°C-130°C.
  • the latent hardener is substantially inactive at room temperature but be capable of activation at temperatures above 50°C to effect the heat cure of the epoxy resin.
  • Suitable hardeners are described in British Patent No. 1,121,196 (Ciba Geigy AG), European Patent Application No. 138465A (Ajinomoto Co.) or European Patent Application No. 193068A (Asahi Chemical), the disclosure of each of which are hereby expressly inco ⁇ orated herein by reference.
  • hardeners for use herein include commercially available ones, such as Anchor Chemical 2014.
  • British Patent No. 1,121,196 describes a reaction product of phthalic anhydride and an aliphatic polyamine, more particularly a reaction product of approximately equimolar proportions of phthalic acid and diethylamine triamine.
  • a hardener of this type is available commercially from Ciba Speciality Chemicals under the trade mark CIBA HT 9506.
  • latent hardener is a reaction product of (i) a polyfunctional epoxy compound, (ii) an imidazole compound such as 2-ethyl-4-methylimidazole and (iii) phthalic anhydride.
  • the polyfunctional epoxy compound may be any compound having two or more epoxy groups in the molecule as described in U. S. Patent No. 4,546,155, the disclosure of which is hereby expressly inco ⁇ orated herein by reference.
  • a hardener of this type is commercially available from Ajinomoto Co. Inc. under the trade mark AJICURE PN-23, which is believed to be an adduct of EPON 828 (bisphenol type epoxy resin epoxy equivalent 184-194, commercially available from Resolution Performance), 2-ethyl-4-methylimidazole and phthalic anhydride.
  • hardeners are those given in U. S. Patent No.5,077, 376, and those of the 112 patent termed"amine adduct latent accelerators", or the reaction product of a 19 compound having one or more isocyanate groups in its molecule with a compound having at least one primary or secondary amino group in its molecule.
  • Additional latent hardeners include 2-heptadeoylimidazole, 2-phenyl 4-5dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl- 4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-8-2-methylimidazolyl- (l)-ethyl-5- triazine, additional products of triazine with isocyanuric acid, succinohydrazide, adipohydrazide, isophtholohydrazide, o-oxybenzohydrazide and salicylohydrazide.
  • liquid anhydride hardeners used in underfill type products may also be used.
  • compositions of the present invention are suitable for formulation as one-part compositions.
  • the heat absorbing (or heat sink) material is desirably one that can absorb relatively large amounts of heat.
  • the heat absorbing component has an effective heat capacity such that it absorbs a substantial portion of the heat liberated by the cured epoxy resin.
  • the heat absorbing component undergoes a phase change in the range of temperatures from the cure onset temperature to the end temperature of reaction.
  • the onset temperature is between 50-90°C, more typically between 60-80°C.
  • the temperature for completion of the reaction is typically between 100-200°C, more typically between 100-150°C and more typically between 110-140°C.
  • the heat absorbing component undergoes a phase change from a solid to a liquid as appropriate 20 to the temperature range in question. Normally a "peak exotherm temperature" is reached.
  • the heat absorbing component undergoes melting at a temperature in the range of temperatures between the onset temperature of reaction and the end temperature of reaction of the cure exotherm.
  • the heat absorbing component melts at a temperature within +/- 60 °C of the peak exotherm reached (without the heat absorbing component being present).
  • the melting point of the heat absorbing component may be used to carefully select a heat absorbing component specifically for a particular cure temperature in order to achieve ⁇ H reduction for different cure systems.
  • the heat absorbing component has a melting point in the range of 50° to 200°C, preferably in the range 60 to 180°C, and more preferably in the range 80°C to 150°C.
  • phase change materials include paraffin waxes having a melting point above 250°C or polymer waxes having a melting point in the range 400°C to 1600°C.
  • Other materials which are not generally suitable for inclusion in the composition of the present invention include polyethylene waxes and polypropylene waxes having melting points in the range from 400°C to 1600°C.
  • the particle size of the heat absorbing component may affect the rate of melting and hence the ability of the heat absorbing component to absorb heat evolved from the cure reaction.
  • the heat absorbing component is polythene.
  • the heat absorbing 21 component such as polythene, has a particle size in the range of between 500 micron and 0.001 micron, more preferably between 200 and 0.001 micron and further preferably between 100 and 0.001 micron.
  • the heat absorbing component may be a liquid having a latent heat of vaporisation such that it undergoes a phase change from a liquid to a gas upon absorbing heat generated upon cure of the epoxy resin.
  • compositions of the invention it is desirable to reduce the amount of heat given out by the composition, on curing, to less than 300 J/g. If the amount of heat given out is equal to, or exceeds this value then certain restrictions apply to the shipping of the material as laid out in the United Nations Recommendations on the Transport of Dangerous Goods, Model Regulations, Class 4.1 Self Reactive Substances, Section 2.4.2.3. These restrictions at a minimum can make transportation of a product meeting these criteria from one destination to another be quite cumbersome and oftentimes add significant cost. Thus, it is desirable to avoid said restrictions. Suitably therefore, the heat liberated by the cure reaction of the compositions described herein is less than 300 J/g-
  • the heat absorbing component is unreacted following cure of the curable component (is inert). It is apparent that the cured materials formed by compositions of the present invention include the heat absorbing material trapped physically in the cured composition. It is important for the pu ⁇ oses of the present invention that the material does not become a part of the chemical reaction on curing. The heat absorbing materials of the present invention should be retained dispersed within the cured product in such a way that the material can be separately melted/solidified without affecting the cured composition. This phenomenon can be observed by reheating the cured product of a composition of the invention and considering the temperature change profile of the material. 22 EXAMPLES The invention is described in more detail with reference to the following examples.
  • Example 1 (Control Composition No. 1) A curable composition was prepared by blending an epoxy resin with a latent curing agent.
  • control composition no. 1 was prepared by blending the various epoxy resins and fumed silica under vacuum before addition of the latent hardener Ajicure PN 23.
  • a curable composition was prepared by re-making control composition no. 1 but with the addition of 10 parts by weight of talc.
  • a curable composition was prepared by re-making control composition no. 1 but with the addition of polyethylene (commercially available as Acumist B6, from Nordman and Rassman GmbH) as a low melting point filler.
  • the melting point of the polyethylene used is 120-128*0.
  • Polyethylene was present in an amount of 10 parts by weight.
  • curable composition was prepared by re-making control composition no. 1 but with the addition of polyethylene (commercially available as Acumist B6, from Nordman and Rassman GmbH) as a low melting point filler. Polyethylene was present in an amount of 20 parts by weight.
  • Example 5 (formulation i — Control Composition no.2)
  • control composition of formulation i (control composition no.2) comprising a low temperature cure epoxy adhesive was prepared.
  • a curable composition was prepared by re-making control composition no. 2 but with the addition of Thixcin R (hydrogenated castor oil; supplier Elementis Specialities) as a low melting point filler.
  • Thixcin R hydrogenated castor oil; supplier Elementis Specialities
  • Thixcin R was present in an amount of 10 parts by weight.
  • a curable composition was prepared by re-making control composition no.2 but with the addition of Thixcin R as a low melting point filler.
  • Thixcin R was present in an amount of 20 parts by weight. 25
  • Example 8 (formulation ii - Control Composition ; 0O, .3 )
  • control composition of formulation ii (control composition no. 3) comprising a low temperature cure epoxy adhesive was prepared.
  • the formulation was the same as that of formulation i above. However a different batch was used and was designated "formulation ii”.
  • a curable composition was prepared by re-making control composition no.3 but with the addition of R 2526 (commercially available wax, supplier Moore and Munger Inc.) as a low melting point filler. R 2526 was present in an amount of 5 parts by weight. Component Parts by Weight
  • a curable composition was prepared by re-making control composition no.3 but with the addition of R 2526 (commercially available wax, supplier Moore and Munger Inc.) as a low melting point filler.
  • R 2526 commercially available wax, supplier Moore and Munger Inc.
  • R 2526 was present in an amount of 10 parts by weight.
  • Example 11 (formulation iii - Control Composition no.4)
  • control composition of formulation iii (control composition no. 4) comprising the following raw materials was prepared.
  • a curable composition was prepared by re-making control composition no. 4 but with the addition of Paraflint C 80 (commercially available wax, supplier Schumann Sasol) as a low melting point filler. Paraflint C 80 was present in an amount of 10 parts by weight.
  • a curable composition was prepared by re-making control composition no.4 but with the addition of Paraflint SP 30 F (commercially available wax, supplier Schumann Sasol) as a low melting point filler. SP 30 F was present in an amount of 20 parts by weight.
  • a curable composition was prepared by re-making control composition no. 4 but with the addition of R 2542 (commercially available wax, supplier Moore and Munger Inc.) 28 as a low melting point filler.
  • R 2542 commercially available wax, supplier Moore and Munger Inc. 28 as a low melting point filler.
  • R 2542 was present in an amount of 10 parts by weight.
  • Example 15 (formulation iv — Control Composition no. 5)
  • control composition of formulation iv (control composition no.5) comprising the following raw materials was prepared.
  • a curable composition was prepared by re-making control composition no.5 but with the addition of talc as a low melting point filler. Talc was present in an amount of 20 parts by weight. 29
  • a curable composition was prepared by re-making control composition no.5 but with the addition of polyethylene (commercially available as Acumist B6, from Nordman and Rassman GmbH) as a low melting point filler. Polyethylene was present in an amount of
  • curable compositions were prepared in order to test the effect of the inclusion of elemental sulphur on the exotherm of the composition.
  • Figure 1 shows a DSC curve for a sample of epoxy adhesive composition from Example 1.
  • the composition does not contain a heat absorbing material.
  • the onset temperature of reaction is shown to be 72°C with a maximum temperature of reaction of 119.48°C.
  • the ⁇ H value was determined to be 337.33 J/g.
  • Figure 2 shows a DSC curve for a sample of the epoxy composition from Example 2 which includes talc as a heat absorbing component.
  • the amount of talc inco ⁇ orated in the composition was 10 parts by weight.
  • the presence of talc in the adhesive composition was found to reduce the ⁇ H value to 309.33 J/g.
  • the DSC for the sample of the composition of Example 3 shows a decrease in the ⁇ H value as compared to that of Example 1.
  • the composition of Example 3 includes 10 parts by weight polyethylene.
  • the DSC illustrates the effect of the presence of polyethylene on the exotherm of the cure reaction.
  • the ⁇ H value was determined to be 266-53 J/g.
  • the DSC for a sample of the composition of Example 4 demonstrates a significant decrease in the value of the enthalpy of reaction when compared to that observed for the composition as prepared in Example 1.
  • the composition of Example 4 which included 20 parts by weight of polyethylene, resulted in a ⁇ H value of 216.28 J/g. 32
  • the inco ⁇ oration of a heat absorbing material has been found to cause a reduction of the ⁇ H value of the cure reaction.
  • the enthalpy of reaction values ⁇ H R obtained for the compositions of Examples 3 and 4 demonstrate a significant decrease in the exotherm value as compared to the value for the composition of Example 1 and Example 2.
  • compositions 3 and 4 of a heat absorbing material (filler material) selected to have a melting point close to the peak cure temperature of the control (unfilled) sample 1 is shown to cause a decrease in the value of the enthalpy of reaction of at least 20-35% when compared to the enthalpy of reaction of the composition of Example 1.
  • Example 2 also contains a heat absorbing material but not one which has been selected for the coincidence of its melting point with the peak cure temperature.
  • the composition of example 2 contains talc which has a melting point of 1500°C.
  • Tables 2 to 5 illustrate the exotherm values observed when DSC scans were run on compositions having different curing profiles to those in Table 1.
  • Formulations i and ii are low temperature cure epoxy adhesives with a typical polymerisation onset temperature of 80-90°C, a peak polymerisation temperature of 90- 100°C and a large exotherm value of greater than 300 J/g.
  • Table 2 illustrates the effect of hydrogenated castor oil, Thixcin R (melting point 85- 88°C) on the exotheim of the composition of formulation i (control composition no. 2).
  • Formulation i (control composition no. 2) has a ⁇ H value of 376.85 J/g.
  • the presence of Thixcin R in 10 parts by weight reduces the ⁇ H value to 332.49 J/g.
  • the composition of Example 7 (formulation i with 20 parts by weight of Thixcin R ) has a ⁇ H value of 310.22 J/g.
  • Table 3 demonstrates the effect of selecting a heat absorbing component having an unsuitable melting point, that is, a melting point that is not coincident with the exotherm profile of the adhesive composition.
  • Formulation ii (control composition no.3) has a ⁇ H value of 356.86 J/g.
  • Table 3 demonstrates that the presence of a wax, R 2526, (commercially available from Moore & Munger Inc.) has no substantial effect on the exotherm value of the composition of formulation ii. It is believed that this is due to the fact that the melting point of the wax R 2526 (m.pt.51.7-54.4°C) is below the onset temperature of polymerisation. The wax has already melted by the time the adhesive starts to cure.
  • Formulations iii and iv have a different cure profile to formulations i and ii in Tables 2 and 3 above.
  • Formulations iii and iv have cure onset temperatures of 75-81 °C and peak polymerisation temperatures of 120-122 °C.
  • the results in Table 4 illustrate how the presence of a heat absorbing component having a melting point coincident with the cure exotherm profile of the control adhesive composition can reduce the exotherm value of the composition.
  • the results also demonstrate that the inclusion of a heat absorbing component having a melting point outside the curing temperature range of the control composition does not reduce the exotherm of the composition significantly.
  • composition comprising 10 parts by weight of Paraflint C 80 has an exotherm value of 281.61 J/g whereas the composition comprising 10 parts by weight of the wax R 2542 has an exotherm value of 318.68 J/g.
  • Table 4
  • a DSC scan was run on each of the cured samples of the scanned compositions from Examples 3 and 4 to ensure that the samples were fully cured.
  • Example 4 With reference to Figure 5, the cured composition from Example 3 was re-scanned.
  • the DSC demonstrated an endothermic peak corresponding to the melting temperature of the polyethylene with a ⁇ H value of 20-30 J/g.
  • a similar DSC demonstrating an endothermic peak was observed for the re-scanned cured sample from Example 4.
  • the glass transition temperature (Tg) was measured on a Dynamic Mechanical Thermal Analyser (DMTA) according to ASTM E 1640: Standard Test Method for Assignment of the Glass Transition Temperature by Dynamic Mechanical Analysis.
  • the tensile shear of the cured adhesive samples was measured according to ASTM D 1002: Standard Test Method for Apparent Shear Strength of Single Lap Joint Adhesively Bonded Metal Specimens By Tension Loading (Metal-to-Metal).
  • the polyethylene does not appear to adversely affect the cured properties when added to the adhesive composition as a heat absorbing material.
  • the polyethylene used in the Examples above has a melting point 110-120°C, and ⁇ Hf US j on value of 98J/g.
  • the glass transition temperature or tensile shear strength is not significantly affected when levels of polyethylene less than 20 parts by weight are added.
  • the invention describes an epoxy composition which includes an epoxy resin, a latent curing agent and a heat absorbing component.
  • the heat absorbing component is suitably selected on the basis of its melting point being coincident with the cure exotherm temperature of the original composition.
  • the heat absorbing material undergoes melting in the temperature range of the exotherm profile of the adhesive composition.
  • the results demonstrate that the inclusion of a heat absorbing material having a melting point range in the exotherm profile of the adhesive composition, results in a more efficient reduction in the total exotherm.
  • the decrease in ⁇ H value can be explained as follows. As the epoxy composition containing the heat absorbing material (filler) is heated, the epoxy starts to cure and liberates heat. Some of the heat generated is absorbed by the heat absorbing component, which undergoes fusion (melting). As the adhesive cures the exotherm is reduced by the corresponding amount of heat absorbed by the heat absorbing component during the melting process.
  • the non melting heat absorbing (filler) component is limited in its ability to reduce the exotherm by the heat capacity of the particular (filler) material selected. Such materials also only usually 38 become effective at high levels, whereby the levels are chosen on the basis that the number of epoxy groups in the formulation is being reduced and this has the effect of reducing the exotherm value.
  • Figures 1-4 and Figures 7-19 illustrate the effects of the inclusion of inert heat absorbing materials such as talc, polyethylene and certain commercially available waxes on the exotherm of an epoxy composition.
  • the compositions tested demonstrated that heat absorbing materials having a lower melting point, in particular those with melting points in the temperature range of the cure exotherm of the adhesive are more efficient at absorbing heat.
  • Traditional heat absorbing materials such as talc have a low heat capacity and greater quantities are required to be added to the composition in order to effectively reduce the exotherm value. As a result these materials are not efficient heat absorbing materials. Such large quantities can undesirably affect other properties of the adhesive such as viscosity, adhesion or Tg (glass transition temperature), for example.
  • the adhesive control composition number 1 used in the compositions described herein has a ⁇ H value > 300J/g when used in the absence of a heat absorbing material.
  • the compositions according to the invention were found to have a reduced exotherm value.
  • Table 1 the reduction of the ⁇ H value for the composition containing talc was not as significant as the reduction observed for the composition of Example 3.
  • Polyethylene was found to be an effective heat absorbing component as the exotherm value for the compositions of Examples 3 and 4 was reduced by 20% and 35% respectively.
  • the polyethylene undergoes an endothermic phase transition upon re-scanning a cured sample of the compositions of Examples 3 and 4.
  • the polyethylene does not react. It merely undergoes a phase transition and changes from a solid to a liquid (melting).
  • the polyethylene solidifies and is dispersed in the composition.
  • the polyethylene re-melts as demonstrated by the endotherm profile shown in Figures 5 and 6. This demonstrates that the polyethylene does not take part in the cure reaction.
  • the reduced exotherm values of the compositions described herein, in particular those in Table 1 are desirable as they fall outside of the ranges for exotherm values of compositions which are subject to stringent requirements for shipping.
  • UN Model regulations state that self reactive substances must be shipped in specially adapted UN approved cartons.
  • Self-reactive substances are defined as " thermally unstable substances liable to undergo a strongly exothermic decomposition even without the participation of oxygen". Substances are not considered to be self reactive 40 substances if, their heat of decomposition is less than 300 J/g or their SADT (self accelerating decomposition temperature) is greater than 75 deg C for a 50 kg package .
  • the one part curable exothermic formulations described herein, and in particular those referred to in Table 1 have a ⁇ H value less than 300 J/g and are therefore not classified as self-reactive substances and therefore do not require UN classification/testing. These compositions can therefore be shipped without restriction and without the need for specially adapted packaging (as described in European patent EP 0 908 399), thereby minimising high costs associated with the transport of such materials.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une composition réticulable sélectionnée dans le groupe constitué par des adhésifs, des produits d'étanchéité et des revêtements. Cette composition contient: (i) un composant réticulable; (ii) un agent de réticulation pour faire réticuler le composant réticulable, la réticulation étant exothermique; et (iii) un composant inerte absorbant la chaleur et dispersé dans la composition pour absorber la chaleur générée par la réaction exothermique en une quantité suffisante pour réaliser au moins une des conditions sélectionnées dans le groupe de conditions comprenant: (a) la chaleur dégagée par la réaction diminue d'au moins 10 %, la quantité de composant absorbant la chaleur étant inférieure à 20 % en poids de la composition totale; et/ou (b) le composant absorbant la chaleur a un point de fusion dans la plage de températures allant de la température de début de réticulation à la température finale de la réaction; et/ou (c) la chaleur dégagée par la réaction est réduite d'au moins 10 joules par gramme de la composition totale, la quantité de composant absorbant la chaleur étant inférieure à 20 % en poids de la composition totale. Ces compositions sont peu exothermiques, leur dégagement de chaleur étant inférieur ou égal à 300 J/g.
PCT/IE2004/000099 2003-08-14 2004-07-21 Compositions reticulables a enthalpie reduite Ceased WO2005016987A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/026,221 US20080177023A1 (en) 2003-08-14 2008-02-05 Curable compositions having a reduced enthalpy output

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IE2003/0601 2003-08-14
IE20030601A IE20030601A1 (en) 2003-08-14 2003-08-14 Curable compositions having a reduced enthalpy output

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/056,093 Continuation US20050239922A1 (en) 2003-08-14 2005-02-14 Curable compositions having a reduced enthalpy output

Publications (1)

Publication Number Publication Date
WO2005016987A1 true WO2005016987A1 (fr) 2005-02-24

Family

ID=34113372

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IE2004/000099 Ceased WO2005016987A1 (fr) 2003-08-14 2004-07-21 Compositions reticulables a enthalpie reduite

Country Status (3)

Country Link
US (2) US20050239922A1 (fr)
IE (1) IE20030601A1 (fr)
WO (1) WO2005016987A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007050520A3 (fr) * 2005-10-24 2007-06-21 Bayer Materialscience Llc Compositions de polyurethane solides, et procedes de reparation d'infrastructures et de stabilisation geographique
WO2009129084A1 (fr) * 2008-04-14 2009-10-22 Dow Global Technologies Inc. Utilisation d’une matière de charge qui subit une transition de phase endothermique pour abaisser la chaleur exothermique de réaction de compositions à base d’époxyde
KR101432393B1 (ko) * 2012-12-28 2014-08-20 삼성전기주식회사 지자기 센서 모듈 밀봉용 에폭시 수지 조성물 및 이로 밀봉된 지자기 센서 모듈
WO2018077411A1 (fr) * 2016-10-27 2018-05-03 Kordsa Teknik Tekstil Anonim Sirketi Mélanges d'agents d'arrêt d'exothermie

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8796137B2 (en) * 2010-06-24 2014-08-05 Stats Chippac, Ltd. Semiconductor device and method of forming RDL along sloped side surface of semiconductor die for z-direction interconnect
DE102013102725A1 (de) * 2013-03-18 2014-09-18 Deutsches Zentrum für Luft- und Raumfahrt e.V. Reaktionsharzsystem
WO2023059154A1 (fr) * 2021-10-08 2023-04-13 주식회사 엘지화학 Composition durcissable

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0908399A1 (fr) * 1997-10-10 1999-04-14 National Starch and Chemical Investment Holding Corporation Système d'emballage et méthode pour l'expédition de matériaux exothermiques
JP2000053944A (ja) * 1998-06-04 2000-02-22 Hitachi Kasei Polymer Co Ltd 熱硬化型発泡性シ―ル材組成物
WO2000035997A1 (fr) * 1998-12-11 2000-06-22 Woodbridge Foam Corporation Mousse de polymere a base d'isocyanate et processus de production

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2061801A1 (fr) * 1991-02-26 1992-08-27 Yasushi Sawamura Resine d'epoxy pour encapsuler les dispositifs a semiconducteur
US5597886A (en) * 1994-03-10 1997-01-28 Ciba-Geigy Corporation Heat-curable epoxy resin systems having a good reactivity/stability ratio
US6121348A (en) * 1995-11-18 2000-09-19 Ciba Specialty Chemicals Corp. Powderable reactive resin compositions
US6099894A (en) * 1998-07-27 2000-08-08 Frisby Technologies, Inc. Gel-coated microcapsules
US6703442B1 (en) * 1999-03-24 2004-03-09 Kaneka Corporation Two-pack type curable composition and hardener therefor
US6548575B2 (en) * 2000-12-13 2003-04-15 National Starch And Chemical Investment Holding Corporation High temperature underfilling material with low exotherm during use
US6519968B1 (en) * 2001-05-09 2003-02-18 Loctite Corporation Shipping container for exothermic material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0908399A1 (fr) * 1997-10-10 1999-04-14 National Starch and Chemical Investment Holding Corporation Système d'emballage et méthode pour l'expédition de matériaux exothermiques
JP2000053944A (ja) * 1998-06-04 2000-02-22 Hitachi Kasei Polymer Co Ltd 熱硬化型発泡性シ―ル材組成物
WO2000035997A1 (fr) * 1998-12-11 2000-06-22 Woodbridge Foam Corporation Mousse de polymere a base d'isocyanate et processus de production

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 200020, Derwent World Patents Index; Class A21, AN 2000-233151, XP002299171 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007050520A3 (fr) * 2005-10-24 2007-06-21 Bayer Materialscience Llc Compositions de polyurethane solides, et procedes de reparation d'infrastructures et de stabilisation geographique
WO2009129084A1 (fr) * 2008-04-14 2009-10-22 Dow Global Technologies Inc. Utilisation d’une matière de charge qui subit une transition de phase endothermique pour abaisser la chaleur exothermique de réaction de compositions à base d’époxyde
US20110077328A1 (en) * 2008-04-14 2011-03-31 Ludovic Valette Use of filler that undergoes endothermic phase transition to lower the reaction exotherm of epoxy based compositions
CN102007158B (zh) * 2008-04-14 2014-06-25 陶氏环球技术公司 经历吸热相变以降低基于环氧树脂的组合物的反应放热量的填料的应用
KR101432393B1 (ko) * 2012-12-28 2014-08-20 삼성전기주식회사 지자기 센서 모듈 밀봉용 에폭시 수지 조성물 및 이로 밀봉된 지자기 센서 모듈
WO2018077411A1 (fr) * 2016-10-27 2018-05-03 Kordsa Teknik Tekstil Anonim Sirketi Mélanges d'agents d'arrêt d'exothermie

Also Published As

Publication number Publication date
IE20030601A1 (en) 2005-02-23
US20080177023A1 (en) 2008-07-24
US20050239922A1 (en) 2005-10-27

Similar Documents

Publication Publication Date Title
US20080177023A1 (en) Curable compositions having a reduced enthalpy output
AU728193B2 (en) Thermosetting resin compositions useful as underfill sealants
TWI465477B (zh) A liquid cyanate ester - epoxy composite resin composition
EP1047744B1 (fr) Compositions durcissables a base d'epoxy
CN101128502B (zh) 环氧树脂用潜在性固化剂和环氧树脂组合物
EP0659793B1 (fr) Compositions de résine époxyde à un composant contenant des produits d'addition époxyde-amine modifiés comme durcisseurs
Rehman et al. Development of new graphene/epoxy nanocomposites and study of cure kinetics, thermal and mechanical properties
US6887737B1 (en) Epoxidized acetals and thioacetals, episulfidized acetals and thioacetals, and reworkable thermosetting resin compositions formulated therefrom
JP7681289B2 (ja) 樹脂組成物
Sickfeld et al. Application of thermal analysis for the investigation of epoxy resins
WO2012077377A1 (fr) Composition de résine
US3562215A (en) Low temperature,latent epoxy resin curing system
KR102770605B1 (ko) 액체 압축 성형 또는 캡슐화제 조성물
EP1700874B1 (fr) Composition durcissable
KR20210078480A (ko) 수지 조성물
JP2020200389A (ja) 硬化性樹脂組成物
JP2020100684A (ja) 樹脂組成物
JP2022151308A (ja) 熱硬化性接着剤組成物及びその硬化物並びに接合体
Patel et al. Kinetics of thermal degradation of cured epoxy resins based on triglycidyl-p-aminophenol
JPS61183317A (ja) 低温速硬化型エポキシ樹脂組成物
WO2025176980A1 (fr) Formulation adhésive
KR101226662B1 (ko) 비캡슐형 표면 개질 아민계 경화제를 함유한 일액형 에폭시수지 조성물 및 이를 이용한 이방 도전성 접착재료
CN110392709A (zh) 使用金属纳米粒子和含氮催化剂的环氧树脂稳定以及方法
Suttitham Preparation and characterization of sequential curing with off-stoichiometric amine-diglycidyl ether of bisphenol a/novolac epoxy blended systems
WO2025023051A1 (fr) Composition de résine époxy, adhésif, matériau d'étanchéité, produit durci, dispositif à semi-conducteur, et composant électronique

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase